JPS62260719A - Production of transition metal polysulfide complex of former period and production thereof - Google Patents
Production of transition metal polysulfide complex of former period and production thereofInfo
- Publication number
- JPS62260719A JPS62260719A JP10319386A JP10319386A JPS62260719A JP S62260719 A JPS62260719 A JP S62260719A JP 10319386 A JP10319386 A JP 10319386A JP 10319386 A JP10319386 A JP 10319386A JP S62260719 A JPS62260719 A JP S62260719A
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- complex
- transition metal
- polysulfide
- represented
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001021 polysulfide Polymers 0.000 title claims abstract description 50
- 239000005077 polysulfide Substances 0.000 title claims abstract description 50
- 150000008117 polysulfides Polymers 0.000 title claims abstract description 50
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 27
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 27
- -1 transition metal chalcogenide Chemical class 0.000 claims abstract description 20
- 229910001507 metal halide Inorganic materials 0.000 claims abstract description 11
- 150000005309 metal halides Chemical class 0.000 claims abstract description 11
- 239000010955 niobium Substances 0.000 claims abstract description 11
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 12
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical group C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 claims description 9
- 125000005207 tetraalkylammonium group Chemical group 0.000 claims description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical group [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- PJMJFVQKDBRMIP-UHFFFAOYSA-N tetraphenylarsonium Chemical group C1=CC=CC=C1[As+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 PJMJFVQKDBRMIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052719 titanium Chemical group 0.000 claims description 6
- 239000010936 titanium Chemical group 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 150000002366 halogen compounds Chemical class 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical group [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 230000000704 physical effect Effects 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 4
- 150000004820 halides Chemical class 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract 2
- 229910001216 Li2S Inorganic materials 0.000 abstract 1
- 238000000034 method Methods 0.000 description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 229920000592 inorganic polymer Polymers 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000000862 absorption spectrum Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000004770 chalcogenides Chemical class 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- DHBXNPKRAUYBTH-UHFFFAOYSA-N 1,1-ethanedithiol Chemical class CC(S)S DHBXNPKRAUYBTH-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910016323 MxSy Inorganic materials 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 229910019804 NbCl5 Inorganic materials 0.000 description 1
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 150000001787 chalcogens Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- OHZZTXYKLXZFSZ-UHFFFAOYSA-I manganese(3+) 5,10,15-tris(1-methylpyridin-1-ium-4-yl)-20-(1-methylpyridin-4-ylidene)porphyrin-22-ide pentachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mn+3].C1=CN(C)C=CC1=C1C(C=C2)=NC2=C(C=2C=C[N+](C)=CC=2)C([N-]2)=CC=C2C(C=2C=C[N+](C)=CC=2)=C(C=C2)N=C2C(C=2C=C[N+](C)=CC=2)=C2N=C1C=C2 OHZZTXYKLXZFSZ-UHFFFAOYSA-I 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- GCPVYIPZZUPXPB-UHFFFAOYSA-I tantalum(v) bromide Chemical compound Br[Ta](Br)(Br)(Br)Br GCPVYIPZZUPXPB-UHFFFAOYSA-I 0.000 description 1
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
- 150000007944 thiolates Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は前用ｊｔＪ］遷移金属ポリスルフィド錯体およ
びその製造方法に関し、詳しくは新規な前周期遷移金属
ポリスルフィド錯体ならびにその効率のよい製造方法に
関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a pre-transition metal polysulfide complex and a method for producing the same, and more particularly to a novel pre-transition metal polysulfide complex and an efficient method for producing the same.
〔従来の技術および発明が解決しようとする問題点〕ニ
オブ、タンタル等の前周期遷移金属のカルコゲニド化合
物は、特有の電磁気的性質等、興味深い物性を示す無機
高分子化合物であり、最近様々な分野で注目を浴びてき
ている。[Prior art and problems to be solved by the invention] Chalcogenide compounds of early transition metals such as niobium and tantalum are inorganic polymer compounds that exhibit interesting physical properties such as unique electromagnetic properties, and have recently been used in various fields. has been attracting attention.
しかし、これまでのところ上述の無機高分子化合物を製
造するには、前周期遷移金属の粉末とカルコゲンを７昆
合したものを５００〜１０００℃およびそれ以上の高温
下で同相反応させる方法に限られていた。しかも、この
固相反応によって得られる無機高分子化合物は、必ずし
も所望する物性を示さず、実用的価値のあるものはなか
なか製造することができなかった。However, to date, the production of the above-mentioned inorganic polymer compounds has been limited to a method in which a mixture of early transition metal powder and chalcogen is subjected to an in-phase reaction at high temperatures of 500 to 1000°C or higher. It was getting worse. Moreover, the inorganic polymer compounds obtained by this solid-phase reaction do not necessarily exhibit desired physical properties, and it has been difficult to produce ones with practical value.
また、本発明者らは先般、上述の無機高分子化合物の新
しい製造方法として、モノマーに相当するエタンジチオ
ラート錯体を合成し、これを熱分解ｑて無機高分子化す
る方法を開発した（特願昭６０−２２２７１９号明細書
）。この方法により製造される無機高分子化合物は、熱
分解条件を選定することにより、希望する電気伝導度を
付与することができるものである。しかしながら、この
無機高分子化合物には、チオラートやカチオン種に由来
する炭素や水素が１０〜２０％程度残存するという問題
がある。In addition, the present inventors have recently developed a method for synthesizing ethanedithiolate complexes corresponding to monomers and thermally decomposing them into inorganic polymers as a new method for producing the above-mentioned inorganic polymer compounds (particularly Application No. 60-222719). The inorganic polymer compound produced by this method can be given a desired electrical conductivity by selecting the thermal decomposition conditions. However, this inorganic polymer compound has a problem in that about 10 to 20% of carbon and hydrogen derived from thiolate and cation species remain.
そこで本発明者らは、さらに研究を進め、上述の方法の
欠点を解消し、全く新たな方法で効率よくしかも物性の
すくれた上記無機高分子化合物である前周期遷移金属カ
ルコゲニドを製造すべく検討を重ねた。Therefore, the present inventors conducted further research, and aimed to overcome the drawbacks of the above-mentioned methods and to efficiently produce the above-mentioned early transition metal chalcogenide, which is an inorganic polymer compound with poor physical properties, using a completely new method. After much consideration.
その結果、特定の金属ポリスルフィド錯体を熱分解する
ことにより、目的とする物性の前周期遷移金属カルコゲ
ニドを製造することに成功した。As a result, we succeeded in producing early transition metal chalcogenide with the desired physical properties by thermally decomposing a specific metal polysulfide complex.
また、その研究過程において、本発明者らは上述の熱分
解原料として、全く新たな金属錯体を開発することにも
成功した。In addition, in the course of the research, the present inventors also succeeded in developing a completely new metal complex as the above-mentioned thermal decomposition raw material.
本発明の目的は、すぐれた物性を有する無機高分子化合
物たる前周期遷移金属カルコゲニドの製造原料として有
用な新規な金属錯体を提供すること、およびこの錯体の
を効な製造方法を提供することにある。The purpose of the present invention is to provide a novel metal complex useful as a raw material for producing an early transition metal chalcogenide, which is an inorganic polymer compound having excellent physical properties, and to provide an effective method for producing this complex. be.
すなわち本発明は、
一般式
％式％（１）
（式中、Ｍはニオブ、ジルコニウム、バナジウム、タン
タルあるいはチタンを示し、Ａはリチウム、テトラフェ
ニルホスホニラ１１゜テ１−ラフェニルアルソニウムあ
るいはテトラアルキルアンモニウムを示す。また、Ｘ＋
Ｙは正の実数を示す。）
で表わされる前用！ｔＪＩ遷移金属ポリスルフィド↑１
￥体を提供するものであり、またこの一般式（１）で表
わされる前周！ｔ１１遷移金９ポリズルフィド錯体を製
造する方法として、一般式ＭＸ’、（式中、Ｍは前記と
同じであり、ＸＩはハロゲン原子を示す。That is, the present invention is based on the general formula % (1) (where M represents niobium, zirconium, vanadium, tantalum or titanium, and A represents lithium, tetraphenylphosphonyl 11°te 1-raphenylarsonium or tetra Indicates alkylammonium.Also, X+
Y indicates a positive real number. ) is represented by the previous use! tJI transition metal polysulfide ↑1
It provides the ¥ body, and the front circumference expressed by this general formula (1)! As a method for producing a t11 transition gold 9-polysulfide complex, the general formula MX' (wherein M is the same as above and XI represents a halogen atom) is used.
ｍはＭの原子価を示す。）で表わされるハロゲン化金属
および一般式ＬｉｚＳｍ（式中、ａは１〜５の実数を示
す。）で表わされるリチウムポリスルフィドを反応させ
る方法（以下「方法１」という。m indicates the valence of M. ) and lithium polysulfide represented by the general formula LizSm (in the formula, a represents a real number from 1 to 5) (hereinafter referred to as "Method 1").
ならびに一般式ＭＸ’ｆｆ１Ｃ式中、Ｍ 、 Ｘ ’
、 ｍは前記と同じ。）で表わされるハロゲン化金属、
一般式Ｌｉ２Ｓａ（式中、ａは前記と同じ。）で表わさ
れるリチウムポリスルフィドおよび一般式ＱＸ２（式中
、Ｑはテトラフェニルホスホニウム。and in the general formula MX'ff1C, M, X'
, m are the same as above. ) metal halide represented by
Lithium polysulfide represented by the general formula Li2Sa (wherein a is the same as above) and general formula QX2 (wherein Q is tetraphenylphosphonium).
テトラフェニルアルソニウムまたはテトラアルキルアン
モニウムを示し、Ｘ２はハロゲン原子を示す。）で表わ
されるハロゲン化合物を反応させる方法（以下「方法２
」という。）を提供するものである。It represents tetraphenylarsonium or tetraalkylammonium, and X2 represents a halogen atom. ) (hereinafter referred to as "Method 2")
”. ).
前記一般的（１）で表わされる本発明の前周期遷移金属
ポリスルフィド錯体は炭素と水素を含まない可溶性キレ
ート型ポリスルフィド錯体であり、この錯体において、
Ｍはニオブ、ジルコニウム。The early transition metal polysulfide complex of the present invention represented by general (1) above is a soluble chelate type polysulfide complex that does not contain carbon and hydrogen, and in this complex,
M is niobium and zirconium.
バナジウム、タンクルあるいはチタンのいずれかの前周
期遷移金属であり、Ａはリチウム（Ｌｉ）。It is an early transition metal such as vanadium, tanker, or titanium, and A is lithium (Li).
テトラフェニルホスホニウム（（Ｃ６Ｈ５）ＪＰ））
。Tetraphenylphosphonium ((C6H5)JP))
.
テトラフェニルアルソニウム（（Ｃ６Ｈｓ）４ＡＳ）
あるいはテトラアルキルアンモニウム（Ｒ４Ｎ）で）、
ある。またｘ、ｙは必ずしも整数に限られず、正の実数
であればよく特に限定はないが、通常はｙとＸのモル比
ｙ／ｘとして２〜４である。このポリスルフィド錯体の
具体例をあげれば、Ａがリチウムの場合には、Ｌｉ （
Ｎｂ３Ｓ＋ｚ）などがあり、またＡがテトラフェニルホ
スホニウムの場合には、（（Ｃ６Ｈ５）４Ｐ）［Ｎｂｚ
Ｓｚｚ）などがある。Tetraphenylarsonium ((C6Hs)4AS)
or with tetraalkylammonium (R4N)),
be. Further, x and y are not necessarily limited to integers, and may be any positive real number and are not particularly limited, but the molar ratio y/x of y and X is usually 2 to 4. To give a specific example of this polysulfide complex, when A is lithium, Li (
Nb3S+z) etc., and when A is tetraphenylphosphonium, ((C6H5)4P)[Nbz
Szz) etc.
前述した本発明の方法１によれば、−Ｃ式Ａ （ＭＸＳ
ｙ）で表わされる前周期遷移金属ポリスルフィド錯体の
うち、Ａがリチウムである一般式Ｌ ｉ （Ｍ ＸＳ
ｙ ）で表わされる錯体が得られる。この方法１によっ
て上記前周期遷移金属ポリスルフィド錯体を製造するに
は、前周期遷移金属のハロゲン化物（ハロゲン化金属）
とリチウムポリスルフィドを反応させればよい。ここで
ハロゲン化金属は一般式ＭＸ’、で表わされるものであ
り、具体的にはＮｂＣｌ５＋ ＮｂＢｒ５．ＺｒＣ１ｎ
＋ ＺｒＢｒａｔＶ Ｃｌ３． Ｖ Ｂｒ３． Ｔ
ａＣｌ５． ＴａＢｒ５． ＴｌＣ１４゜Ｔ ｉ Ｂ
ｒ ａなどがあげられる。According to method 1 of the present invention described above, -C formula A (MXS
Among the early transition metal polysulfide complexes represented by y), the general formula Li (M
A complex represented by y) is obtained. In order to produce the above-mentioned early transition metal polysulfide complex by this method 1, a halide (metal halide) of an early transition metal is used.
and lithium polysulfide. Here, the metal halide is represented by the general formula MX', specifically NbCl5+ NbBr5. ZrC1n
+ ZrBratV Cl3. VBr3. T
aCl5. TaBr5. TlC14゜T i B
Examples include ra.
一方、リチウムポリスルフィドは一般式ｔ、ｔ２ｓａで
表わされるものであり、具体的には通常はＬ ｉｚ Ｓ
ａ 、 Ｌ ｉｚ Ｓ ｓがあげられるが、またＬ
ｉｚＳ、 Ｉ、１ｚＳｚ、ＬｉｚＳ３などもある。さ
らに上記化合物の混合物の場合はａは非整数となる。On the other hand, lithium polysulfide is represented by the general formula t, t2sa, and specifically, it is usually L iz S
a, L iz S s, but also L
There are also izS, I, 1zSz, LizS3, etc. Further, in the case of a mixture of the above compounds, a is a non-integer.
なお、このリチウムポリスルフィドは金属リチウムと単
体いおうを液体アンモニウム中で撹拌するなどの方法で
得ることができる。Note that this lithium polysulfide can be obtained by a method such as stirring metallic lithium and elemental sulfur in liquid ammonium.
上述の方法１は、ハロゲン化金属とリチウムポリスルフ
ィドを反応させることによって進行するが、この際溶媒
としてアセトニトリルを用いることが好ましく、アセト
ニトリル存在下で上記反応を行なうと効率よく進行する
。また、この際の反応温度は特に制限はなく、所望する
部間３ｔＪＩ遷移金属ポリスルフィド錯体の種類等によ
り異なるが、一般には−４０°Ｃ〜＋５０°Ｃ１好まし
くはｏ ’ｃ〜２０℃程度の範囲に設定すればよい。さ
らに、反応の際に加えるハロゲン化金属とリチウムポリ
スルフィドの量比についても、ｆ！Ａ造すべきポリスル
フィド錯体の種類に応じて定めればよく、特に制限はな
い。Method 1 described above proceeds by reacting a metal halide with lithium polysulfide, and in this case, it is preferable to use acetonitrile as a solvent, and the reaction proceeds efficiently when carried out in the presence of acetonitrile. In addition, the reaction temperature at this time is not particularly limited and varies depending on the type of the desired interpartial 3tJI transition metal polysulfide complex, etc., but is generally in the range of -40°C to +50°C, preferably about o'c to 20°C. You can set it to . Furthermore, regarding the quantitative ratio of metal halide and lithium polysulfide added during the reaction, f! A may be determined depending on the type of polysulfide complex to be produced, and is not particularly limited.
次に、本発明の方法２によれば一般式Ａ（Ｍ、ｓ、）で
表わされる前周期遷移金属ポリスルフィド錯体のうち、
Ａがテトラフェニルホスホニウムである一般式 （（Ｃ
６１（Ｓ）４Ｐ）（Ｍ、Ｓｙ）の錯体、Ａかテトラフェ
？ラルソニウムである一般式（（Ｃ６Ｈ５）４Ａｓ）（
ＭｘＳｙ〕の錯体、あるいはＡがテトラアルキルアンモ
ニウムである一般式（Ｒ，Ｎ）（ＭＸＳ、）（式中、Ｒ
はアルキル基）の錯体が得られる。この方法２によって
、前周間遷移金属ポリスルフィド錯体を製造するには、
前述のハロゲン化金属とリチウムポリスルフィドととも
に、ハロゲン化合物、具体的にはハ［２ゲン化テトラフ
エニルホスホニウム、ハロケン化テトラフェニルアルソ
ニウムあるいはハロゲン化テトラアルキルアンモニウム
を反応させｎ、ぽよい。ここでハロゲン化金属およびリ
チウムポリスルフィドの具体例としては前述した如きも
のがあげられる。Next, according to method 2 of the present invention, among the early transition metal polysulfide complexes represented by the general formula A (M, s,),
General formula where A is tetraphenylphosphonium ((C
61(S)4P)(M,Sy) complex, A or tetraphe? Larsonium has the general formula ((C6H5)4As)(
MxSy] or a complex of the general formula (R,N) (MXS, ) in which A is tetraalkylammonium (wherein R
is an alkyl group). To produce a preperitoneal transition metal polysulfide complex by this method 2,
A halogen compound, specifically, tetraphenylphosphonium halide, tetraphenylarsonium halide, or tetraalkylammonium halide, is reacted with the aforementioned metal halide and lithium polysulfide. Specific examples of the metal halide and lithium polysulfide include those mentioned above.
また、ハロゲン化テトラフェニルホスホニウムは−Ｓ式
（Ｃ６Ｈ５）４ＰＸ”で表わされるものであり、具体的
には（Ｃ６Ｈ５）４ＰＢｒ、（Ｃ６Ｈｓ）４ＰＣＩがあ
げられる。ハロゲン化テトラフェニルアルソニウムは一
般式（Ｃｂ Ｈｓ ） ４ Ａ ｓ Ｘ ”で表わされ
、具体的には（Ｃ６Ｈ５）４ＡＳ Ｃｊ！＋ （ＣｈＨ
ｓ）４ＡｓＢｒなどがあげられ、ハロゲン化テトラアル
キルアンモニウムは一般式Ｒ４ＮＸ”で表わされ、具体
的には（ＣｚＨｓ）ａＮｃｌ、（ＣｚＨｓ）ａＮＢｒ。Furthermore, halogenated tetraphenylphosphonium is represented by the formula -S (C6H5)4PX", and specific examples include (C6H5)4PBr and (C6Hs)4PCI. Halogenated tetraphenylarsonium is represented by the general formula ( Cb Hs ) 4 A s X ”, specifically (C6H5)4AS Cj! + (ChH
s) 4AsBr, etc., and the tetraalkylammonium halide is represented by the general formula R4NX'', specifically (CzHs)aNcl, (CzHs)aNBr.
（Ｃ４Ｈ９）ＮＣＲ，ＣＣａＨｑ）ＮＢｒなどがあげら
れる。Examples include (C4H9)NCR, CCaHq)NBr, and the like.
上述の方法２は、ハロゲン化金属、リチウムポリスルフ
ィドおよびハロゲン化テトラフェニルホスホニウム（あ
るいはハロゲン化テトラフェニルアルソニウムやハロゲ
ン化テトラアルキルアンモニウム）を同時に反応系に加
えて反応を進行させてもよく、また前記方法１にて一般
式Ｌｉ（Ｍ、Ｓ、）をつくり、さらにこれにハロゲン化
テトラフェニルホスホニウム（あるいはハロゲン化テト
ラフェニルアルソニウムやハロゲン化テトラアルキルア
ンモニウム）を反応させることによって進行させてもよ
い。いずれの場合においても反応は溶媒としてのアセト
ニトリルの存在下で進行させることが好ましく、また、
この際の反応１品度や各層ｆ：）の使用割合については
、前記方法１に準ずればよく、特に制限はない。In the above method 2, the reaction may proceed by simultaneously adding a metal halide, lithium polysulfide, and tetraphenylphosphonium halide (or tetraphenylarsonium halide or tetraalkylammonium halide) to the reaction system, or the above method. The reaction may be carried out by preparing the general formula Li (M, S,) in Method 1 and further reacting it with a halogenated tetraphenylphosphonium (or a halogenated tetraphenylarsonium or a halogenated tetraalkylammonium). In any case, the reaction is preferably carried out in the presence of acetonitrile as a solvent, and
At this time, the quality of the reaction and the proportion of each layer f:) to be used may be in accordance with Method 1, and there are no particular limitations.
なお、方法２によって得られる一般式
（（Ｃ６Ｈ５）４Ｐ）（ＭＸｓｙ）で表わされる錯体（
錯体のＰｈ４Ｐ塩）は、一般式Ｌ ｉ （Ｍ ＸＳ ｙ
）で表わされる錯体（錯体のＬ ｉ塩）よりも空気中に
おいてやや安定に存在するものである。In addition, the complex represented by the general formula ((C6H5)4P)(MXsy) obtained by method 2 (
Ph4P salt of the complex) has the general formula L i (M XS y
) exists slightly more stably in the air than the complex (Li salt of the complex).
上述の方法１あるいは方法２によれば、前記したような
一般式（Ｉ）で表わされるような前周期遷移金属ポリス
ルフィド錯体の結晶が得られるが、さらにこの結晶をジ
メチルホルムアミド（ＤＭＦ）等の溶媒に溶解し、再結
晶を行なえば一層純度の高い錯体が得られる。According to Method 1 or Method 2 described above, crystals of the early transition metal polysulfide complex represented by the general formula (I) as described above can be obtained, but these crystals are further treated in a solvent such as dimethylformamide (DMF). A more pure complex can be obtained by dissolving it in and recrystallizing it.
本発明の方法１，２によれば、高い収率でしかも高純度
の前回！ｔＪＩ遷移金属ポリスルフィド錯体が得られる
。また、この錯体は、簡単な熱分解反応によって、ニオ
ブカルコゲニド、ジルコニウムカルコゲニド、バナジウ
ムカルコゲニド、タンタンカルコゲニド、チタンカルコ
ゲニドという金属カルコゲニドと称される電気伝導性の
良好な無機高分子化合物となる。特に、この場合に得ら
れる無機高分子化合物は、炭素や水素等の不純物の極め
て少ないものとなる。According to methods 1 and 2 of the present invention, high yield and high purity can be obtained! A tJI transition metal polysulfide complex is obtained. Further, through a simple thermal decomposition reaction, this complex becomes inorganic polymer compounds with good electrical conductivity called metal chalcogenides such as niobium chalcogenide, zirconium chalcogenide, vanadium chalcogenide, tantanum chalcogenide, and titanium chalcogenide. In particular, the inorganic polymer compound obtained in this case contains extremely few impurities such as carbon and hydrogen.
したがって、本発明の前周期遷移金属ポリスルフィド錯
体は、良好な電気伝導性を示す無機高分子化合物の製造
原料として有効に利用することができる。Therefore, the early transition metal polysulfide complex of the present invention can be effectively used as a raw material for producing an inorganic polymer compound exhibiting good electrical conductivity.
［実施例］ 次に本発明を実施例によりさらに詳しく説明する。[Example] Next, the present invention will be explained in more detail with reference to Examples.
なお、以下の操作はすべてアルゴン雰囲気下、あるいは
真空下で行ない、また溶媒は充分に乾燥した後、アルゴ
ン雰囲気下で蒸留して使用した。All of the following operations were performed under an argon atmosphere or under vacuum, and the solvent was thoroughly dried and then distilled under an argon atmosphere before use.
参考例１（リチウムポリスルフィド（ＬｉｚＳ４）の合
成）金属リチウム０．６６ｇ（９５ミリモル）と単体イ
オウ（Ｓ原子すなわち１／８３８として） ６．１ ｇ
（１９０ミリモル）を５００ｍｆｆ三つロフラスコに入
れ、メカニカルスタラーを取り付けた。反応系を一７８
℃にした後、攪拌しながらアンモニアガスを吹き込んだ
ところ、橙褐色の溶液が生成した。液体アンモニアが約
２００ｍｌになるまでアンモニアガスを吹き込み、その
後、冷媒を取り除き、室温でアンモニアを留去した。約
３時間後にはアンモニアは留去され、橙褐色の固体が得
られた。これをさらに減圧下で一晩乾燥しアンモニアを
除いた。容器の底にへばりつくようにしてリチウムポリ
スルフィド（ＬｉｚＳｎ） ７．２ ｇが得られた。Reference Example 1 (Synthesis of lithium polysulfide (LizS4)) 0.66 g (95 mmol) of metallic lithium and 6.1 g of elemental sulfur (S atom, that is, 1/838)
(190 mmol) was placed in a 500 mff three-neck flask and equipped with a mechanical stirrer. The reaction system is 78
After bringing the temperature to ℃, ammonia gas was blown into the mixture while stirring, and an orange-brown solution was produced. Ammonia gas was blown into the reactor until the liquid ammonia amounted to about 200 ml, then the refrigerant was removed, and the ammonia was distilled off at room temperature. After about 3 hours, ammonia was distilled off and an orange-brown solid was obtained. This was further dried under reduced pressure overnight to remove ammonia. 7.2 g of lithium polysulfide (LizSn) was obtained so that it stuck to the bottom of the container.
参１１１２ ＜リチウムポリスルフィド頁ＬｉｚＳｓ）
の合成）参考例１において、単体イオウ（Ｓ原子すなわ
ち１／８Ｓｅとして）を７．６ｇ（２４０ミリモル）と
したｊこヒ以外は、参考例Ｉと同様の操作を行なって、
リチウムポリスルフィド（ＬｉｚＳｓ）を高収率で得た
。Reference 1112 <Lithium polysulfide page LizSs)
Synthesis) In Reference Example 1, the same operation as in Reference Example I was carried out, except that 7.6 g (240 mmol) of elemental sulfur (S atom, that is, 1/8 Se) was used.
Lithium polysulfide (LizSs) was obtained in high yield.
実施例１
参考例２で得られたリチウムポリスルフィド（Ｌ ｉｚ
Ｓ ｓ’） ６．３ ｇ （３６，２ミリモル）のア
セトニトリル溶液１００ｍｌに、五塩化ニオブ（ＮｂＣ
１，）２．９ｇ（１０，７ミリモル）のアセトニトリル
溶液６０ｍ１水浴中で滴下した。数分で溶液の色は褐色
から緑に変わった。そのまま−晩撹拌した。その後褐色
の沈殿（ＬｉＣ１，Ｎｂを含む分解物）を濾過により取
除いた後、アセトニトリルを減圧下で留去し、緑色ター
ル状の固体（ポリスルフィド錯体Ｌｉ （Ｎｂ３Ｓ、□
））５．８ｇを得た。Example 1 Lithium polysulfide (Liz
S s') 6.3 g (36.2 mmol) of niobium pentachloride (NbC
1.) A solution of 2.9 g (10.7 mmol) of acetonitrile was added dropwise in a 60 ml water bath. The color of the solution changed from brown to green in a few minutes. The mixture was stirred overnight. After that, the brown precipitate (decomposed product containing LiCl, Nb) was removed by filtration, and the acetonitrile was distilled off under reduced pressure.
)) 5.8g was obtained.
実施例２
上記実施例１で得られた固体にテトラフェニルホスホニ
ウムブロマイド（Ｃ６Ｈ５）４Ｐ Ｂ ｒ ４． ｌ’
ｇ（１０ミリモル）のアセトニトリル溶液（２０ｍｊり
を少量ずつ加えて攪拌し、−晩冷蔵庫に静置して粗結晶
を得、さらにこれを常法により精製して結晶３．５ｇを
得た。このものの分析結果は次のとおりであった。Example 2 Tetraphenylphosphonium bromide (C6H5)4P B r was added to the solid obtained in Example 1 above. l'
(10 mmol) of acetonitrile solution (20 mj) was added little by little, stirred, and left to stand in the refrigerator overnight to obtain crude crystals, which were further purified by a conventional method to obtain 3.5 g of crystals. The analysis results were as follows.
遠赤外吸収スペクトル（Ｎｕｊｏｌ ｍｕｌｌ、 ｃｍ
−’）４９２ｍ、 ３６９ｍ、 ３５０ｍ、 ３
２５ｍ。Far infrared absorption spectrum (Nujol mull, cm
-') 492m, 369m, 350m, 3
25m.
２９０ｗｗ、 ２６７ｗ、 １８７Ｗ紫外−可視吸
収スペクトル（λｍａｘ、 ｎｍ）ＣＴＩ３ＣＮ溶液５
Ｇ０．６１２；
Ｃ１１：ｌＯＨ溶ン（１３１８，３８０ｓｈ、 ４
３０ｓｈこれらの結果および元素分析の結果から、上記
結晶は組成式（（Ｃ６Ｈ５）４Ｐ）ＣＮｈ３Ｓ＋□〕で
表わされるポリスルフィド錯体であることがわかった。290ww, 267w, 187W UV-visible absorption spectrum (λmax, nm) CTI3CN solution 5
G0.612; C11:1OH soluble (1318,380sh, 4
From these results and the results of elemental analysis, it was found that the above crystal was a polysulfide complex represented by the compositional formula ((C6H5)4P)CNh3S+□].
実施例３
参考例１で得られたリチウムポリスルフィド（Ｌｊ２５
４） ６．６ ｇ（４４゜６ミリモル）と四塩化ジルコ
ニウム（ＺｒＣＩ４） ３．４ ｇ （１４，８ｇミ
リ、ユ
モル）をアセトニトリル中にて室温１時間反応させて橙
色のポリスルフィド錯体Ｌｉ （ＺｒＸＳ、）６．６ｇ
を得た。この錯体はアセトニトリルやジメチルホルムア
ミド
るが、これはＳ３−の色である。またこの錯体はメタノ
ールに熔けて黄色溶液になった。なお、このものの分析
結果（紫外−可視吸収スペクトル）は次の通りであった
。Example 3 Lithium polysulfide obtained in Reference Example 1 (Lj25
4) 6.6 g (44°6 mmol) and 3.4 g (14.8 g mmol) of zirconium tetrachloride (ZrCI4) were reacted in acetonitrile at room temperature for 1 hour to form an orange polysulfide complex Li (ZrXS, )6.6g
I got it. This complex is made of acetonitrile or dimethylformamide, and this is the color of S3-. This complex also dissolved in methanol to form a yellow solution. The analysis results (ultraviolet-visible absorption spectrum) of this product were as follows.
紫外−可視吸収スペクトル（λｍａｘ， ｎｍ）ｃ Ｈ
、Ｏ Ｈ ？８液 ４ ０ ２実施例４
三塩化バナジウム（ＶＣＩ：ｌ） ２．４ ｇ （１
５ミリモル）のアセトニトリル懸濁液を、参考例１で得
られたリチウムポリスルフィド（ＬｉｚＳａ） ４．
２ ｇ（３０．２ミリモル）のアセトニトリル懸濁液に
加えたところ、液の色が橙褐色から濃褐色に変化した。Ultraviolet-visible absorption spectrum (λmax, nm) c H
,OH? 8 liquid 4 0 2 Example 4 Vanadium trichloride (VCI:l) 2.4 g (1
5 mmol) of acetonitrile suspension was mixed with the lithium polysulfide (LizSa) obtained in Reference Example 1.
When it was added to a suspension of 2 g (30.2 mmol) in acetonitrile, the color of the liquid changed from orange-brown to dark brown.
１時間攪拌した後、不溶物を濾過し、減圧下で溶媒を留
去したところ、黒色ガラス状の固体（ポリスルフィド錯
体Ｌ ｉ （ Ｖ ＸＳ ｙ））６． ２ ｇが得られ
た。この生成物はアセトニトリルやＤＭＦに溶−は緑色
の溶液を与え、またメタノールに溶は黄色の溶液になっ
た。なお、このものの分析結果（紫外−可視吸収スペク
トル）は次のとおりであった。After stirring for 1 hour, insoluble matter was filtered and the solvent was distilled off under reduced pressure, resulting in a black glassy solid (polysulfide complex Li (V XS y))6. 2 g was obtained. This product gave a green solution when dissolved in acetonitrile or DMF, and a yellow solution when dissolved in methanol. The analysis results (ultraviolet-visible absorption spectrum) of this product were as follows.
紫外−可視吸収スペクトル（λｍａｘ， ｎｍ）Ｃ Ｈ
：ｌＯ Ｈ ？８液 ２’５ ６， ３ ５
７， ４ ５ ０ｓｈ。Ultraviolet-visible absorption spectrum (λmax, nm) C H
:lOH? 8 liquid 2'5 6, 3 5
7,450sh.
４ ９ ０ｓｈ， ５ ９ ０ｓｈ， ６ ５ ０
ｓｈ実施例５
参考例１で得られたリチウムポリスルフィド（ＬｉｚＳ
４） ６． ６ ｇ （ ４４． ６ミリモル）と五塩
化タンクル（Ｔａｃｌｓ） ５． ７ ｇ （ １
５． ６ミリモル）幸
をアセトニトリルにて室温１時間反応させて赤褐色のポ
リスルフィド錯体ｉ体Ｌｉ （Ｔａ．ｓ，） ６． ８
ｇを得た。4 9 0sh, 5 9 0sh, 6 5 0
sh Example 5 Lithium polysulfide (LizS) obtained in Reference Example 1
4) 6. 6 g (44.6 mmol) and Tacls pentachloride 5. 7 g (1
5. 6 mmol)) was reacted with acetonitrile at room temperature for 1 hour to obtain a reddish brown polysulfide complex i-form Li (Ta.s,) 6. 8
I got g.
このｔａ体はアセトニトリルやり． Ｍ Ｆに溶は緑色
溶液となり、またメタノールに）容けて赤褐色）各機に
なった。なお、このものの分析結果（紫外−可視吸収ス
ペクトル）は次の通りであった。This ta body is acetonitrile. When dissolved in MF, it became a green solution, and when dissolved in methanol, it became a reddish brown solution. The analysis results (ultraviolet-visible absorption spectrum) of this product were as follows.
紫外−可視吸収スペクトル（λｍａｘ， ｎｍ）Ｃ Ｈ
：ｌＯ Ｈｍ？ｆｆｌ ３ １ ０ ｓｈ， ３ ７
０ ｓｈ。Ultraviolet-visible absorption spectrum (λmax, nm) C H
:lO Hm? ffl 3 1 0 sh, 3 7
0 sh.
２０ｓｈ １・１己−・ニーへ１20sh 1・1self-・neeto1
Claims (8)
タルあるいはチタンを示し、Ａ はリチウム、テトラフェニルホスホニウム、テトラフェ
ニルアルソニウムあるいはテト ラアルキルアンモニウムを示す。また、ｘ、ｙは正の実
数を示す。） で表わされる前周期遷移金属ポリスルフィド錯体。(1) General formula A [M_xS_y] (wherein M represents niobium, zirconium, vanadium, tantalum, or titanium; A represents lithium, tetraphenylphosphonium, tetraphenylarsonium, or tetraalkylammonium; x, (y is a positive real number.) An early transition metal polysulfide complex represented by:
ニウム、バナジウム、タンタルあるいはチタンを示し、
Ｘ＾１はハロゲン原子を示す。ｍはＭの原子価を示す。 ）で表わされるハロゲン化金属および一般式Ｌｉ＿２Ｓ
ａ（式中、ａは１〜５の実数を示す。）で表わされるリ
チウムポリスルフィドを反応させることを特徴とする 一般式 Ｌｉ〔Ｍ＿ｘＳ＿ｙ〕 （式中、Ｍは前記と同じであり、ｘ、ｙは正の実数を示
す。） で表わされる前周期遷移金属ポリスルフィド錯体の製造
方法。(2) General formula MX^1_m (where M represents niobium, zirconium, vanadium, tantalum or titanium,
X^1 represents a halogen atom. m indicates the valence of M. ) and the general formula Li_2S
General formula Li[M_xS_y] characterized by reacting lithium polysulfide represented by a (wherein a represents a real number of 1 to 5) (wherein M is the same as above, x, y is a positive real number.) A method for producing an early period transition metal polysulfide complex.
の範囲第２項記載の製造方法。(3) The manufacturing method according to claim 2, wherein the reaction is carried out in the presence of acetonitrile.
ニウム、バナジウム、タンタルあるいはチタンを示し、
Ｘ＾１はハロゲン原子を示す。ｍはＭの原子価を示す。 ）で表わされるハロゲン化金属、一般式Ｌｉ＿２Ｓａ（
式中、ａは１〜５の実数を示す。）で表わされるリチウ
ムポリスルフィドおよび一般式ＱＸ＾２（式中、Ｑはテ
トラフェニルホスホニウム、テトラフェニルアルソニウ
ムまたはテトラアルキルアンモニウムを示し、Ｘ＾２は
ハロゲン原子を示す。）で表わされるハロゲン化合物を
反応させることを特徴とする。 一般式 Ｑ〔Ｍ＿ｘＳ＿Ｙ〕 （式中、Ｑ、Ｍは前記と同じであり、ｘ、ｙは正の実数
を示す。） で表わされる前周期遷移金属ポリスルフィド錯体の製造
方法。(4) General formula MX^1_m (where M represents niobium, zirconium, vanadium, tantalum or titanium,
X^1 represents a halogen atom. m indicates the valence of M. ), a metal halide represented by the general formula Li_2Sa (
In the formula, a represents a real number from 1 to 5. ) and a halogen compound represented by the general formula QX^2 (wherein, Q represents tetraphenylphosphonium, tetraphenylarsonium, or tetraalkylammonium, and X^2 represents a halogen atom). It is characterized by causing A method for producing an early transition metal polysulfide complex represented by the general formula Q [M_xS_Y] (wherein Q and M are the same as above, and x and y represent positive real numbers).
の範囲第４項記載の製造方法。(5) The manufacturing method according to claim 4, wherein the reaction is carried out in the presence of acetonitrile.
一般式（Ｃ＿６Ｈ＿５）＿４ＰＸ＾２で表わされるハロ
ゲン化テトラフェニルホスホニウムである特許請求の範
囲第４項記載の製造方法。(6) The halogen compound represented by the general formula QX^2 is
The manufacturing method according to claim 4, which is a halogenated tetraphenylphosphonium represented by the general formula (C_6H_5)_4PX^2.
一般式（Ｃ＿６Ｈ＿５）＿４ＡｓＸ＾２で表わされるハ
ロゲン化テトラフェニルアルソニウムである特許請求の
範囲第４項記載の製造方法。(7) The halogen compound represented by the general formula QX^2 is
The manufacturing method according to claim 4, which is a tetraphenylarsonium halide represented by the general formula (C_6H_5)_4AsX^2.
一般式Ｒ＿４ＮＸ＾２（式中、Ｒはアルキル基を示す。 ）で表わされるハロゲン化テトラアルキルアンモニウム
である特許請求の範囲第４項記載の製造方法。(8) The halogen compound represented by the general formula QX^2 is
The manufacturing method according to claim 4, which is a halogenated tetraalkylammonium represented by the general formula R_4NX^2 (wherein R represents an alkyl group).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10319386A JPS62260719A (en) | 1986-05-07 | 1986-05-07 | Production of transition metal polysulfide complex of former period and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10319386A JPS62260719A (en) | 1986-05-07 | 1986-05-07 | Production of transition metal polysulfide complex of former period and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62260719A true JPS62260719A (en) | 1987-11-13 |
Family
ID=14347678
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10319386A Pending JPS62260719A (en) | 1986-05-07 | 1986-05-07 | Production of transition metal polysulfide complex of former period and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62260719A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014148432A1 (en) * | 2013-03-18 | 2014-09-25 | 独立行政法人産業技術総合研究所 | Lithium titanium sulfide, lithium niobium sulfide, and lithium titanium niobium sulfide |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5278793A (en) * | 1975-12-17 | 1977-07-02 | Exxon Research Engineering Co | Chalcogenite and its manufacturing process |
-
1986
- 1986-05-07 JP JP10319386A patent/JPS62260719A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5278793A (en) * | 1975-12-17 | 1977-07-02 | Exxon Research Engineering Co | Chalcogenite and its manufacturing process |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014148432A1 (en) * | 2013-03-18 | 2014-09-25 | 独立行政法人産業技術総合研究所 | Lithium titanium sulfide, lithium niobium sulfide, and lithium titanium niobium sulfide |
| JP6011989B2 (en) * | 2013-03-18 | 2016-10-25 | 国立研究開発法人産業技術総合研究所 | Lithium titanium sulfide, lithium niobium sulfide and lithium titanium niobium sulfide |
| US10090524B2 (en) | 2013-03-18 | 2018-10-02 | National Institute Of Advanced Industrial Science And Technology | Lithium titanium sulfide, lithium niobium sulfide, and lithium titanium niobium sulfide |
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